CN106757367B - The preparation method of high length-diameter ratio nickel sulfide monocrystal nano line array - Google Patents
The preparation method of high length-diameter ratio nickel sulfide monocrystal nano line array Download PDFInfo
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- CN106757367B CN106757367B CN201710003161.XA CN201710003161A CN106757367B CN 106757367 B CN106757367 B CN 106757367B CN 201710003161 A CN201710003161 A CN 201710003161A CN 106757367 B CN106757367 B CN 106757367B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention discloses a kind of preparation methods of high length-diameter ratio NiS monocrystal nano line array, belong to function nano technical field of material.This method is using thiocarbamide as sulphur source, using pyridine as reaction dissolvent, has the high length-diameter ratio NiS monocrystal nano line array of good chemical property using solvent-thermal method preparation.Method is simple, high-efficient, at low cost, the high length-diameter ratio NiS monocrystal nano line array of preparation, about 30 nanometers of diameter, about 2 microns of length, draw ratio 67:1, has preferable electrochemical capacitance performance.
Description
Technical field
The present invention relates to a kind of preparation methods of high length-diameter ratio nickel sulfide (NiS) monocrystal nano line array, belong to function and receive
Rice technical field of material.
Background technique
With the increase of the fast development of global economy, the consumption of fossil fuel and environmental pollution, there is an urgent need to one kind
Efficiently, energy is converted and stored to cleaning, the sustainable energy and new technology.In many application fields, most effective and tool
The electrochemical energy conversion of practical technique and storage device are battery, fuel cell and electric chemical super capacitor.Due to it
The cycle life of high power density, length and (high to traditional capacitor (high-output power) and battery/fuel cell is present in
Energy storage) between energy gap have bridging functionality, in recent years people start pay high attention to electric chemical super capacitor,
The architectural characteristic of middle electrode material is to influence the key factor of electric chemical super capacitor performance.Orderly nano array structure by
Make it that there is more application advantage in supercapacitor field in its special design feature, it is specific as follows: (1) nano-array
It is the structure of porous opening, electrolyte osmosis can be promoted to inside, the diffusion path of ion is shortened, to improve system
Dynamic property.In addition, open space can also be used as a powerful reservoir ion, to guarantee to store the institute that reacts
The enough energy needed.(2) nano-array is capable of providing the high-speed channel that an electronics and charge are effectively stored and conveyed.(3)
Conductive substrates are directly contacted with each nano wire, are avoided using polymeric binder and conductive agent, are greatly reduced electrode
" dead zone ", ensure that application of the nano-array electrode material in terms of electrochemistry.Therefore, the nanometer battle array of different materials is synthesized
Array structure is simultaneously used as electrode material for super capacitor and has become current research hotspot.In addition, in metal sulfide,
Ni-S series compound is a kind of semiconductor material with important research value, these Ni-S compounds not only have different
Stoichiometric ratio, such as NiS, Ni3S2、Ni6S5、Ni7S6、Ni9S8、Ni3+xS2Deng, and there is unique physicochemical characteristics, such as
High electron conductivity is easily-synthesized, is at low cost.Therefore, has the Ni-S series compound nanometer battle array of different-shape and composition at present
Array structure is synthesized, and has studied corresponding chemical property, such as: Ni3S2Nano-wire array, NiS nano-tube array,
NiS nano-chip arrays etc..However, being had not been reported about the synthesis of NiS monocrystal nano line array and the research of chemical property.
Therefore, research and develop a kind of simplicity, method preparation NiS monocrystal nano line array at low cost will be to electric chemical super capacitor field
Development have very important significance.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of high length-diameter ratio NiS monocrystal nano line arrays
Preparation method.
Purpose to realize the present invention, the present invention is using thiocarbamide as sulphur source, using pyridine as reaction dissolvent, using nickel foam as nickel source and
Collector prepares the NiS monocrystal nano line array of high length-diameter ratio using solvent-thermal method.
Sulphur source is dissolved in pyridine by this method first, prepares reaction solution, and prepared reaction solution is then carried out solvent heat
Processing controls reaction temperature and time, high length-diameter ratio NiS monocrystal nano line array can be obtained.Especially by following steps reality
It is existing:
1) preparation of chemical reaction liquid: sulphur source is dissolved in pyridine, reaction solution is configured to；Wherein sulphur source is in reaction solution
Concentration be 0.7~1.0 mol L-1；
2) prepared by high length-diameter ratio NiS monocrystal nano line array: pretreated nickel foam being first put into autoclave
In, then by above-mentioned prepared reaction solution immigration, reacted under the conditions of 170-190 DEG C, naturally cool to room temperature after reaction,
Nickel foam is taken out, alternately rinses vacuum drying for several times, i.e. acquisition high length-diameter ratio NiS nanometer monocrystalline with dehydrated alcohol, distilled water
Linear array.
In the invention, nickel foam serves both functions: (1) providing nickel source needed for forming NiS monocrystal nanowire；(2)
In subsequent electrochemical performance study, it is used as collector derived from charge, having a size of 1 × 3~2 × 5 cm2。
In the method for the present invention, the sulphur source is thiocarbamide, and the nickel source is nickel foam.The mass ratio of thiocarbamide and nickel foam
Range is 9~5:1.
Advantage of the present invention and innovative point are as follows:
1. making high length-diameter ratio NiS monocrystal nano line array in preparation due to using nickel foam as nickel source and collector
Save the cost in the process；In electrochemical property test, make NiS nano line array electrode that there is preferable electric conductivity.2. due to
Present invention employs step solvent-thermal method reactions, and raw material is cheap, easy to operate, at low cost, high-efficient, the high length-diameter ratio of preparation
NiS monocrystal nano line array, about 30 nanometers of nanowire diameter, about 2 microns of length, draw ratio 67:1, while having preferable
Electrochemical capacitance performance is 20 mA/cm in current density2When specific capacitance be up to 10.3 F/cm2。
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum for the product that the nickel foam sur-face peeling that the embodiment of the present invention 1 synthesizes gets off；In figure,
1- is the present invention, and 2- is the NiS of standard tripartite；
Fig. 2 is the stereoscan photograph of 1 gained high length-diameter ratio NiS monocrystal nano line array of the embodiment of the present invention.
Fig. 3 is the high-resolution-ration transmission electric-lens photo of 1 gained high length-diameter ratio NiS monocrystal nano line array of the embodiment of the present invention,
Spacing of lattice in figure between two white lines is 0.298nm.
Fig. 4 is the electrode of super capacitor electricity based on 2 gained high length-diameter ratio NiS monocrystal nano line array of the embodiment of the present invention
Chemical property: a) difference sweeps the cyclic voltammograms under speed, and 1,2,3,4,5 respectively represent 3 mVs in figure-1, 5 mVs-1, 7 mVs-1, 10 mVs-1, 20 mVs-1；B) the constant current charge-discharge figure under different current densities, 1,2,3,4,5 respectively represent electricity in figure
Current density is 20 mA/cm2, 25 mA/cm2, 30 mA/cm2, 40 mA/cm2With 50 mA/cm2。
Specific embodiment
It is as follows for embodiment for the present invention is better described, following examples be to it is of the invention furtherly
It is bright, and do not limit the scope of the invention.
Embodiment 1
1. being added to the thiocarbamide of 1.8269 g in the pyridine of 24 mL in the beaker of a 100mL, magnetic agitation is simultaneously
Keep 30 minutes to being completely dissolved.
2. by 1 × 5 pretreated cm2Nickel foam is put into 30mL polytetrafluoroethylliner liner autoclave, then will
1. reaction solution that step is prepared moves into, and at 180 DEG C after solvent heat treatment 9 hours, reaction kettle naturally cools to room temperature, takes out bubble
Foam nickel is alternately rinsed for several times with dehydrated alcohol, distilled water, and vacuum dried sample can be obtained high length-diameter ratio NiS monocrystal nanowire
Array.
The X ray diffracting spectrum for the product that the nickel foam sur-face peeling of synthesis gets off is as shown in Fig. 1, as seen from the figure, institute
There is diffraction maximum to comply fully with the NiS structure (JPCDS NO. 12-41) of standard tripartite, belongs toR3mSpace group does not detect other
Impurity such as Ni9S8、 Ni3S2Deng the peak of other sulfide, show the pure crystalline of product.Attached drawing 2 is that gained high length-diameter ratio NiS is mono-
The stereoscan photograph of brilliant nano-wire array.As seen from the figure, products therefrom is typical nanowire structure, and nanowire diameter
About 30 nanometers, about 2 microns of length, draw ratio 67:1.Fig. 3 is the high score of gained high length-diameter ratio NiS monocrystal nano line array
Distinguish transmission electron microscope photo, clearly lattice fringe shows that gained NiS nano wire is mono-crystalline structures.
Embodiment 2
1. being added to the thiocarbamide of 1.2788 g in the pyridine of 24 mL in the beaker of a 100mL, magnetic agitation is simultaneously
Keep 30 minutes to being completely dissolved.
2. by 1 pretreated × 3cm2Nickel foam is put into the autoclave of 30mL polytetrafluoroethylliner liner, then will
1. reaction solution that step is prepared moves into, and at 190 DEG C after solvent heat 10 hours, reaction kettle naturally cools to room temperature, takes out foam
Nickel, with dehydrated alcohol, distilled water, alternately punching is washed for several times, and vacuum dried sample can be obtained high length-diameter ratio NiS nanometer monocrystalline linear array
Column.
Gained is grown in the high length-diameter ratio NiS monocrystal nano line array of nickel foam as electrode of super capacitor, and is surveyed
Try its electrochemical properties.Fig. 4 a is that the electrode of super capacitor based on high length-diameter ratio NiS monocrystal nano line array sweeps speed in difference
Under cyclic voltammogram, as seen from the figure, which shows a pair of apparent redox peaks, this shows that high length-diameter ratio NiS receives
Rice noodles are a kind of typical fake capacitance materials.Fig. 4 b is constant current charge-discharge figure of the electrode under different current densities, can be with
It was found that each charging and discharging curve has a platform, the characteristic of its fake capacitance material has been reconfirmed, according to the meter of specific capacitance
Calculate formula:, whereinC (F/cm2) it is face capacitor, IIt (A) is discharge current, Δt(s) it is
Discharge time, ΔVIt (V) is voltage window, S (cm2) be electrode work area, it can be deduced that high length-diameter ratio NiS monocrystalline
Nano line array electrode is 20,25,30,40 and 50 mA/cm in current density2When, specific capacitance difference 10.3,
9.1,7.7,7.0 with 6.2 F/cm2, show preferable electrochemical capacitance characteristic.
Embodiment 3
1. being added to the thiocarbamide of 1.8269 g in the pyridine of 24 mL in the beaker of a 100mL, magnetic agitation is simultaneously
Keep 30 minutes to being completely dissolved.
2. by 2 pretreated × 4cm2Nickel foam is put into the autoclave of 30mL polytetrafluoroethylliner liner, then will
1. reaction solution that step is prepared moves into, and at 170 DEG C after solvent heat 8 hours, reaction kettle naturally cools to room temperature, takes out foam
Nickel, with dehydrated alcohol, distilled water, alternately punching is washed for several times, and vacuum dried sample can be obtained high length-diameter ratio same as Example 1
NiS monocrystal nano line array.
Claims (1)
1. the preparation method of high length-diameter ratio NiS monocrystal nano line array, which is characterized in that realized by following steps:
1) it prepares chemical reaction liquid: sulphur source being dissolved in pyridine, reaction solution is configured to；Wherein concentration of the sulphur source in reaction solution is
0.7~1.0 mol L-1；
2) it synthesizes high length-diameter ratio NiS nano-wire array: first processed nickel foam being put into autoclave, then will be above-mentioned
Prepared reaction solution moves into, and reacts under the conditions of 170-190 DEG C, after reaction, naturally cools to room temperature, nickel foam is taken
Out, vacuum drying for several times, i.e. acquisition high length-diameter ratio NiS nanometer monocrystalline linear array are alternately rinsed with dehydrated alcohol, distilled water respectively
Column；The sulphur source is thiocarbamide, and the quality of thiocarbamide and nickel foam is 9~5:1 than range.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108570710A (en) * | 2018-05-16 | 2018-09-25 | 中国科学院上海微系统与信息技术研究所 | The preparation method of copper whisker |
| CN109628951B (en) * | 2018-10-31 | 2021-01-15 | 中山大学 | Nickel sulfide hydrogen evolution electrocatalyst and preparation method and application thereof |
| CN109553076A (en) * | 2019-01-04 | 2019-04-02 | 安阳师范学院 | Two selenizing of monocrystalline, the three nickel nano-wire array and preparation method thereof of nickel foam support |
| CN111362320B (en) * | 2020-03-13 | 2022-07-19 | 江西师范大学 | Loaded nickel sulfide nanorod material as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201380A (en) * | 2014-08-19 | 2014-12-10 | 北京科技大学 | Preparation method of nano Ni3S2 material with lamellar structure |
| CN105489390A (en) * | 2015-11-27 | 2016-04-13 | 上海应用技术学院 | Preparation method of flower-like nickel sulfide material and application of flower-like nickel sulfide material in super capacitor |
| CN105819512A (en) * | 2016-04-06 | 2016-08-03 | 清华大学 | Quick preparation method of transitional metal sulfide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201380A (en) * | 2014-08-19 | 2014-12-10 | 北京科技大学 | Preparation method of nano Ni3S2 material with lamellar structure |
| CN105489390A (en) * | 2015-11-27 | 2016-04-13 | 上海应用技术学院 | Preparation method of flower-like nickel sulfide material and application of flower-like nickel sulfide material in super capacitor |
| CN105819512A (en) * | 2016-04-06 | 2016-08-03 | 清华大学 | Quick preparation method of transitional metal sulfide |
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